EP0652799A1 - Terminal-group-closed anti-foaming agents. - Google Patents

Terminal-group-closed anti-foaming agents.

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Publication number
EP0652799A1
EP0652799A1 EP93915971A EP93915971A EP0652799A1 EP 0652799 A1 EP0652799 A1 EP 0652799A1 EP 93915971 A EP93915971 A EP 93915971A EP 93915971 A EP93915971 A EP 93915971A EP 0652799 A1 EP0652799 A1 EP 0652799A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
foaming agents
acid
carboxylic acids
polyglycol ethers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP93915971A
Other languages
German (de)
French (fr)
Other versions
EP0652799B1 (en
Inventor
Frank Wangemann
Hans-Christian Raths
Wolfgang Poly
Bert Gruber
Juergen Geke
Bernd Stedry
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Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates

Definitions

  • the invention relates to new end group-capped antifoams which are obtained by completely or partially esterifying fatty alcohol polyglycol ethers with carboxylic acids and to the use of these agents as defoamers in a large number of applications.
  • Another field in which anti-foaming agents are used is the wastewater treatment of sewage treatment plants.
  • air is blown into the wastewater, for example, which ensures intimate mixing and the meeting of the dirt particles with the microorganisms [ChiuZ 25, 87 (1991)].
  • the resulting foam is protein foam in many cases and therefore particularly resistant. Instead of sedimentation, there is an undesired fixing of the solids in and on the foam lamellae, which makes it difficult to separate the sewage sludge.
  • fatty alcohol polyglycol ethers which have been end-capped have proven their worth in recent years. These so-called “mixed ethers” are obtained in the sense of Williason's ether synthesis by reacting fatty alcohol polyglycol ethers with alkyl halides [DE-Cl-37 44 525, Handle].
  • esters of fatty alcohols with di- and polycarbonic acids are also known which act as defoamers. For many applications, however, these products are not sufficiently water-soluble.
  • the object of the invention was therefore to provide new anti-foaming agents, the production of which is free from the disadvantages described.
  • the invention relates to new end-capped anti-foaming agents which are obtained by adding fatty alcohol polyglycol ethers of the formula (I)
  • R 1 for an aliphatic, linear or branched hydrocarbon radical having 1 to 22 carbon atoms and 0, 1 1, 2 or 3 double bonds
  • R- for hydrogen or a Methyl group and n stands for numbers from 1 to 40, esterified with carboxylic acids in the presence of acidic catalysts.
  • esters have a good foam-suppressing action and are sufficiently stable even in an alkaline environment over the usual periods of use. Compared to the mixed topic of the prior art, their production is not associated with the inevitable occurrence of salts. They are also characterized by their particularly easy biodegradability and low fish toxicity.
  • the invention further relates to a process for the preparation of end-capped anti-foaming agents, in which fatty alcohol polyglycol ethers of the formula (I)
  • R 1 is an aliphatic, linear or branched hydrocarbon radical having 1 to 22 carbon atoms and 0, 1, 2 or 3 double bonds
  • R - is hydrogen or a methyl group
  • n is a number from 1 to 40
  • Fatty alcohol polyglycol ethers which are considered as starting materials for the production of the new anti-foaming agents in the sense of the invention, are known substances which are produced industrially by addition of ethylene and / or propylene oxide onto primary alcohols. Depending on the ture of the catalyst used, the products can have a conventional or preferably a narrowed homogeneous distribution.
  • Typical examples are addition products of 1 to 40, preferably 2 to 10, mol of ethylene and / or propylene oxide onto capron alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidylyl alcohol, linolenic alcohol , Arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • Fatty alcohol polyglycol ethers of the formula (I) are preferably used, in which R 1 represents alkyl radicals having 2 to 18, in particular 8 to 18, carbon atoms, R2 represents hydrogen and n represents numbers from 2 to 10.
  • the fatty alcohol polyglycol ethers mentioned can be esterified by aliphatic or aromatic, optionally hydroxyl-substituted carboxylic acids having 6 to 22 carbon atoms.
  • aliphatic carboxylic acids are caproic acid, caprylic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, ricinoleic acid, 12-hydroxyachearic acid Gadoleic acid, behenic acid and erucic acid and their technical mixtures which can be obtained, for example, by pressure splitting of Greases and oils.
  • aromatic carboxylic acids are benzoic acid and the isomeric phthalic acids. Saturated aliphatic carboxylic acids having 8 to 18 carbon atom
  • the esterification of the polyglycol ethers with the carboxylic acids can be carried out in a manner known per se.
  • suitable acidic catalysts are mineral acids, sulfonic acids or acidic ion exchangers. Typical examples are sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid or surfactant sulfonic acids; Tin grinding has also proven itself as a catalyst for the esterification of aromatic carboxylic acids. It is advisable to use the catalysts in amounts of 0.5 to 5% by weight, based on the carboxylic acids.
  • the esterification reaction can be carried out at temperatures from 80 to 120, preferably 90 to 110 ° C. In order to shift the reaction equilibrium to the side of the products, it is advisable to remove the condensation water continuously. If desired, the acid catalyst can be neutralized after the esterification.
  • the new antifoam agents are notable for their foam-suppressing action and good ecotoxicological compatibility.
  • Another object of the invention therefore relates to the use of the end group-sealed anti-foaming agents according to the invention for foam regulation in detergents, dishwashing detergents and cleaners, lacquers and paints, as auxiliaries for the sugar and yeast industry and in the wastewater treatment of sewage treatment plants.
  • the formulation was as foam promoter to 6 wt .-% of an adduct of average 12 mol of ethylene oxide to a Ci2 / L4 Ko ° k s i n f ettam added to 0.25.
  • the mixture was injected through a nozzle into a measuring vessel at a temperature of 31 ° C., pumped around continuously, and the foam height obtained was read off from the liquid phase.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Materials Engineering (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Hydrogenated Pyridines (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Described are terminal-group-closed anti-foaming agents obtained by esterifying with carboxylic acids, in the presence of acid catalysts, fatty-alcohol polyglycol ethers of formula (I) in which R1 is a straight-chain or branched-chain aliphatic hydrocarbon group with 1 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R2 is hydrogen or a methyl group and n is a number from 1 to 40. The products are suitable for use as anti-foaming agents in a large number of applications.

Description

Endgruppenverschlossene Antischaiπππiittel End group capped anti-shelling agents
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft neue endgruppenverschlossene Anti- schaummittel, die man durch vollständige oder teilweise Ver¬ esterung von Fettalkoholpolyglycolethem mit Carbonsäuren erhält sowie die Verwendung dieser Mittel als Entschäumer in einer Vielzahl von Anwendungen.The invention relates to new end group-capped antifoams which are obtained by completely or partially esterifying fatty alcohol polyglycol ethers with carboxylic acids and to the use of these agents as defoamers in a large number of applications.
Stand der TechnikState of the art
Für eine Vielzahl technischer Prozesse stellt die mit dem Einsatz von grenzflächenaktiven Substanzen verbundene Schaum¬ entwicklung ein ernsthaftes Problem dar. Bei der maschinellen Haushaltsreinigung von Geschirr, aber auch der großtechni¬ schen Reinigung von Bier- und Milchflaschen werden beispiels¬ weise pulverförmige oder flüssige alkalische Reinigungsmittel verwendet, die neben Tensiden, Gerüstsubstanzen, Alkalime- tallsilicaten, -carbonaten und/oder -hydroxiden zusätzlich Aktivchlor- oder AktivsauerstoffVerbindungen enthalten. Um ein übermäßiges Schäumen zu verhindern, wird diesen Mitteln in der Regel ein Antischaummittel zugesetzt.The foam development associated with the use of surface-active substances represents a serious problem for a large number of technical processes. In the case of mechanical household cleaning of dishes, but also the large-scale cleaning of beer and milk bottles, powdery or liquid alkaline cleaning agents are used, for example used, which in addition to surfactants, builders, alkali metal silicates, carbonates and / or hydroxides also contain active chlorine or active oxygen compounds. To prevent excessive foaming, an anti-foaming agent is usually added to these agents.
Auch bei der Herstellung von Farben und Lacken, beispiels¬ weise Wasserlacken, beobachtet man die Neigung der wasser- verdünnbaren Bindemittel zu verstärkter Schau-nbildung. Schaum kann hier bereits bei der Vermischung der Rezepturbestand¬ teile entstehen, d. h. beim Anreiben des Lackes durch Ein¬ rühren von Luft, und führt dazu, daß die jeweiligen Anlagen nur mit einem Bruchteil des' zu Verfügung stehenden Volumens gefüllt und betrieben werden können. Auch in diesem Bereich ist die Verwendung von Entschäumern und Entlüftern dringend geboten [Goldschmid . Inform. .66., 9 (1989)].Also in the manufacture of paints and varnishes, for example water-based paints, the tendency of the water- dilutable binders for increased visualization. Foam may here arise already during the mixing of the Rezepturbestand¬ parts, that is, on trituration the lacquer by stirring Ein¬ of air, and causes the respective units can be filled only with a fraction of the 'standing at disposal volume and operated. The use of defoamers and deaerators is also urgently required in this area [Goldschmid. Inform. 66., 9 (1989)].
Ein weiteres Feld, in dem Antischaummittel Einsatz finden, ist die Abwasserbehandlung von Kläranlagen. Beim Belebungs¬ verfahren wird beispielsweise in das Abwasser Luft eingebla¬ sen, wodurch eine innige Durchmischung und das Zusammentref¬ fen der Schmutzteilchen mit den Mikroorganismen sicherge¬ stellt wird [ChiuZ 25, 87 (1991)]. Der hierbei entstehende Schaum ist in vielen Fällen Eiweißschaum und daher besonders beständig. Anstelle einer Sedimentation findet eine uner¬ wünschte Fixierung der Feststoffe in und an den Schaumlamel¬ len statt, was eine Abtrennung des Klärschlamms erschwert.Another field in which anti-foaming agents are used is the wastewater treatment of sewage treatment plants. In the aeration process, air is blown into the wastewater, for example, which ensures intimate mixing and the meeting of the dirt particles with the microorganisms [ChiuZ 25, 87 (1991)]. The resulting foam is protein foam in many cases and therefore particularly resistant. Instead of sedimentation, there is an undesired fixing of the solids in and on the foam lamellae, which makes it difficult to separate the sewage sludge.
In der Vergangenheit hat es nicht an Versuchen gefehlt, für das komplexe Gebiet der Schaumregulierung entsprechende Antischaummittel zur Verfügung zu stellen.In the past there has been no lack of attempts to provide appropriate antifoam agents for the complex field of foam regulation.
Neben den wohlbekannten Schaumregulatoren, wie beispielswei¬ se langkettigen Seifen, Copolymeren des Ethylen- und Propy- lenoxids oder Siliconen, haben sich in den letzten Jahren endgruppenverschlossene Fettalkoholpolyglycolether bewährt. Diese sogenannten "Mischether" werden im Sinne einer Willia - son'sehen Ethersynthese durch Umsetzung von Fettalkoholpoly¬ glycolethem mit Alkylhalogeniden erhalten [DE-Cl-37 44 525, Henkel]. Die Herstellung dieser Stoffe ist jedoch mit zwei Nachteilen behaftet: zum einen findet die Reaktion in Gegen¬ wart stöchiometrischer Mengen eines Alkalihydroxids statt und ist dementsprechend mit einem hohen Salzanfall verbunden, zum anderen erfordert das Arbeiten mit Alkylhalogeniden hohe An¬ forderungen an den Arbeitsschutz.In addition to the well-known foam regulators, such as, for example, long-chain soaps, copolymers of ethylene and propylene oxide or silicones, fatty alcohol polyglycol ethers which have been end-capped have proven their worth in recent years. These so-called "mixed ethers" are obtained in the sense of Williason's ether synthesis by reacting fatty alcohol polyglycol ethers with alkyl halides [DE-Cl-37 44 525, Handle]. However, the production of these substances has two disadvantages: on the one hand, the reaction takes place in the presence of stoichiometric amounts of an alkali metal hydroxide and is accordingly associated with a high salt accumulation, on the other hand, working with alkyl halides makes high demands on occupational safety.
Aus der Deutschen Offenlegungsschrift DE-Al-40 41 184 (BASF) sind ferner Ester von Fettalkoholen mit Di- und Polycarbon- säuren bekannt, die als Entschäumer wirken. Für viele Anwen¬ dungen sind diese Produkte jedoch nicht ausreichend wasser¬ löslich.From German published patent application DE-Al-40 41 184 (BASF), esters of fatty alcohols with di- and polycarbonic acids are also known which act as defoamers. For many applications, however, these products are not sufficiently water-soluble.
Die Aufgabe der Erfindung bestand somit darin, neue Anti¬ schaummittel zur Verfügung zu stellen, deren Herstellung frei von den geschilderten Nachteilen ist.The object of the invention was therefore to provide new anti-foaming agents, the production of which is free from the disadvantages described.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung sind neue endgruppenverschlossene Antischaummittel, die man dadurch erhält, daß man Fettalko- holpolyglycolether der Formel (I)The invention relates to new end-capped anti-foaming agents which are obtained by adding fatty alcohol polyglycol ethers of the formula (I)
R2R2
I R10-(CH2CHO)nH (I)IR 1 0- (CH 2 CHO) n H (I)
in der R1 für einen aliphatischen, linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 22 Kohlenstoffatomen und 0, 1 1, 2 oder 3 Doppelbindungen, R- für Wasserstoff oder eine Methylgruppe und n für Zahlen von 1 bis 40 steht, in Gegen¬ wart saurer Katalysatoren mit Carbonsäuren verestert.in the R 1 for an aliphatic, linear or branched hydrocarbon radical having 1 to 22 carbon atoms and 0, 1 1, 2 or 3 double bonds, R- for hydrogen or a Methyl group and n stands for numbers from 1 to 40, esterified with carboxylic acids in the presence of acidic catalysts.
Überraschenderweise wurde gefunden, daß die endgruppenver- schlossenen Ester über eine gute schaumdämpfende Wirkung verfügen und auch im alkalischen Milieu über übliche Anwen¬ dungszeiträume ausreichend beständig sind. Gegenüber den Mischethem des Stands der Technik ist ihre Herstellung nicht mit dem Zwangsanfall von Salzen verbunden. Zudem zeichnen sie sich durch eine besonders leichte biologische Abbaubarkeit und eine geringe Fischtoxizität aus.Surprisingly, it has been found that the end group-closed esters have a good foam-suppressing action and are sufficiently stable even in an alkaline environment over the usual periods of use. Compared to the mixed topic of the prior art, their production is not associated with the inevitable occurrence of salts. They are also characterized by their particularly easy biodegradability and low fish toxicity.
Ein weiterer Gegenstand der Erfindung betrifft ein Verfahren zur Herstellung von endgruppenverschlossenen Antischaummit- teln, bei dem man Fettalkoholpolyglycolether der Formel (I)The invention further relates to a process for the preparation of end-capped anti-foaming agents, in which fatty alcohol polyglycol ethers of the formula (I)
R2R2
I R10-(CH2CHO)nH (I)IR 1 0- (CH 2 CHO) n H (I)
in der R1 für einen aliphatischen, linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen, R- für Wasserstoff oder eine Methylgruppe und n für Zahlen von 1 bis 40 steht, in Gegen¬ wart saurer Katalysatoren mit Carbonsäuren verestert.in which R 1 is an aliphatic, linear or branched hydrocarbon radical having 1 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R - is hydrogen or a methyl group and n is a number from 1 to 40, in the presence of acidic catalysts esterified with carboxylic acids.
Fettalkoholpolyglycolether, die im Sinne der Erfindung als Ausgangsstoffe zur Herstellung der neuen Antischaummittel in Betracht kommen, stellen bekannte Stoffe dar, die großtech¬ nisch durch Anlagerung von Ethylen- und/oder Propylenoxid an primäre Alkohole hergestellt werden. In Abhängigkeit der Na- tur des verwendeten Katalysators, können die Produkte eine konventionelle oder vorzugsweise auch eine eingeengte Homo¬ logenverteilung aufweisen.Fatty alcohol polyglycol ethers, which are considered as starting materials for the production of the new anti-foaming agents in the sense of the invention, are known substances which are produced industrially by addition of ethylene and / or propylene oxide onto primary alcohols. Depending on the ture of the catalyst used, the products can have a conventional or preferably a narrowed homogeneous distribution.
Typische Beispiele sind Aniagerungsprodukte von 1 bis 40, vorzugsweise 2 bis 10 Mol Ethylen- und/oder Propylenoxid an Capronalkohol, Caprylalkohol, Caprinalkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylal- kohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Li- nolylalkohol, Linolenylalkohol, Arachylalkohol, Gadoleylal- kohol, Behenylalkohol und Erucylalkohol sowie deren tech¬ nische Mischungen, wie sie beispielsweise bei der Hydrierung technischer Fettsäuremethylesterfraktionen oder Aldehyde aus der Roelen'sehen Oxosynthese anfallen.Typical examples are addition products of 1 to 40, preferably 2 to 10, mol of ethylene and / or propylene oxide onto capron alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidylyl alcohol, linolenic alcohol , Arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl ester fractions or aldehydes from Roelen's oxosynthesis.
Vorzugsweise werden Fettalkoholpolyglycolether der Formel (I) eingesetzt, in der R1 für Alkylreste mit 2 bis 18, insbeson¬ dere 8 bis 18 Kohlenstoffatomen, R2 für Wasserstoff und n für Zahlen von 2 bis 10 steht.Fatty alcohol polyglycol ethers of the formula (I) are preferably used, in which R 1 represents alkyl radicals having 2 to 18, in particular 8 to 18, carbon atoms, R2 represents hydrogen and n represents numbers from 2 to 10.
Zur Herstellung der neuen Antischaummittel können die genann¬ ten Fettalkoholpolyglycolether aliphatischen oder aromati¬ schen, gegebenenfalls hydroxysubstituierten Carbonsäuren mit 6 bis 22 Kohlenstoffatomen verestert werden. Typische Bei¬ spiele für aliphatische Carbonsäuren sind Capronsäure, Ca- prylsäure, Isononansäure, Caprinsäure, Laurinsäure, Myristin- säure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostea¬ rinsäure, Ölsäure, Elaidinsäure, Linolsäure, Linolensäure, Ricinolsäure, 12-HydroxyStearinsäure, Arachinsäure, Gadolein- säure, Behensäure und Erucasäure sowie deren technische Mi¬ schungen, die man beispielsweise durch Druckspaltung von Fetten und ölen erhält. Typische Beispiele für aromatische Carbonsäuren sind Benzoesäure und die isomeren Phthalsäuren. Vorzugsweise werden gesättigte aliphatische Carbonsäuren mit 8 bis 18 Kohlenstoffatomen und insbesondere Isononansäure eingesetzt.To produce the new anti-foaming agents, the fatty alcohol polyglycol ethers mentioned can be esterified by aliphatic or aromatic, optionally hydroxyl-substituted carboxylic acids having 6 to 22 carbon atoms. Typical examples of aliphatic carboxylic acids are caproic acid, caprylic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, ricinoleic acid, 12-hydroxyachearic acid Gadoleic acid, behenic acid and erucic acid and their technical mixtures which can be obtained, for example, by pressure splitting of Greases and oils. Typical examples of aromatic carboxylic acids are benzoic acid and the isomeric phthalic acids. Saturated aliphatic carboxylic acids having 8 to 18 carbon atoms and in particular isononanoic acid are preferably used.
Die Veresterung der Polyglycolether mit den Carbonsäuren kann in an sich bekannter Weise erfolgen. Als saure Katalysatoren kommen beispielsweise Mineralsäuren, Sulfonsäuren oder saure Ionenaustauscher in Betracht. Typische Beispiele sind Schwe¬ felsäure, Methansulfonsäure, p-Toluolsulfonsäure oder tensi- dische Sulfosäuren; für die Veresterung aromatischer Carbon¬ säuren hat sich ferner Zinnschliff als Katalysator bewährt. Es empfiehlt sich, die Katalysatoren in Mengen von 0,5 bis 5 Gew.-% - bezogen auf die Carbonsäuren - einzusetzen.The esterification of the polyglycol ethers with the carboxylic acids can be carried out in a manner known per se. Examples of suitable acidic catalysts are mineral acids, sulfonic acids or acidic ion exchangers. Typical examples are sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid or surfactant sulfonic acids; Tin grinding has also proven itself as a catalyst for the esterification of aromatic carboxylic acids. It is advisable to use the catalysts in amounts of 0.5 to 5% by weight, based on the carboxylic acids.
Die Versterungsreaktion kann bei Temperaturen von 80 bis 120, vorzugsweise 90 bis 110°C durchgeführt werden. Um das Reak¬ tionsgleichgewicht auf die Seite der Produkte zu verlagern, empfiehlt es sich, das Kondensationswasser kontinuierlich zu entfernen. Falls gewünscht, kann der saure Katalysator nach der Veresterung neutralisiert werden. The esterification reaction can be carried out at temperatures from 80 to 120, preferably 90 to 110 ° C. In order to shift the reaction equilibrium to the side of the products, it is advisable to remove the condensation water continuously. If desired, the acid catalyst can be neutralized after the esterification.
Gewerbliche AnwendbarkeitIndustrial applicability
Die neuen Antischaummittel zeichnen sich durch eine schaum¬ dämpfende Wirkung und gute ökotoxikologische Verträglichkeit aus.The new antifoam agents are notable for their foam-suppressing action and good ecotoxicological compatibility.
Ein weiterer Gegenstand der Erfindung betrifft daher die Ver¬ wendung der erfindungsgemäßen endgruppenverschlossenen Anti¬ schaummittel zur Schaumregulierung in Wasch-, Spül- und Rei¬ nigungsmitteln, Lacken und Farben, als Hilfsmittel für die Zucker- und Hefeindustrie sowie in der Abwasserbehandlung von Kläranlagen.Another object of the invention therefore relates to the use of the end group-sealed anti-foaming agents according to the invention for foam regulation in detergents, dishwashing detergents and cleaners, lacquers and paints, as auxiliaries for the sugar and yeast industry and in the wastewater treatment of sewage treatment plants.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. The following examples are intended to explain the subject matter of the invention in more detail without restricting it.
BeispieleExamples
Beispiel 1;Example 1;
Herstellung von Octansäure-octanol-4,5 EO-ester. In einem 500-ml-Dreihalskolben mit Rüher und Destillationsaufsatz wur¬ den 163,1 g (0,5 mol) eines Anlagerungsproduktes von durch¬ schnittlich 4,5 mol Ethylenoxid an Octanol mit eingeengter Homologenverteilung (Dehydol(R) 04-NRE, Fa.Henkel KGaA, Düs¬ seldorf/FRG) und 107,4 g (0,75 mol) Octansäure vorgelegt und mit 1,1 g konz. Schwefelsäure versetzt. Die Mischung wurde auf 110°C erhitzt und das Kondensationswasser unter vermin¬ dertem Druck aus dem Gleichgewicht abdestilliert. Nach ca. 160 min wurde der Reaktionsmischung erneut 1,1 g Schwefel¬ säure zugesetzt und weitere 10 min gerührt. Der Octansäure- 4,5 EO-ester wurde in praktisch quantitativer Ausbeute als hellgelbe, leichtbewegliche Flüssigkeit erhalten.Production of octanoic acid-octanol-4,5 EO-ester. In a 500 ml three-necked flask with stirrer and distillation attachment, 163.1 g (0.5 mol) of an adduct of an average of 4.5 mol of ethylene oxide with octanol with a narrow homolog distribution (Dehydol ( R ) 04-NRE, Fa .Henkel KGaA, Düsseldorf / FRG) and 107.4 g (0.75 mol) of octanoic acid and concentrated with 1.1 g of conc. Sulfuric acid added. The mixture was heated to 110 ° C. and the water of condensation was distilled off from the equilibrium under reduced pressure. After about 160 min, 1.1 g of sulfuric acid was again added to the reaction mixture and the mixture was stirred for a further 10 min. The octanoic acid 4.5 EO ester was obtained in practically quantitative yield as a light yellow, easily movable liquid.
Beispiel 2:Example 2:
Anwendungstechnische Prüfung. Die entschäumende Wirkung von Octansäure-octanol-4,5 EO-ester wurde in folgender Rezeptur getestet:Application test. The defoaming effect of octanoic acid-octanol-4,5 EO-ester was tested in the following recipe:
Triethanolamin 30 Gew.-% Octansäure 4 Gew.-%Triethanolamine 30% by weight octanoic acid 4% by weight
Octansäure-octyl-4,5EO-ester 4 Gew.-% Wasser, dest. 62 Gew.-% Der Rezeptur wurde als Schaumpromotor 0,25 bis 6 Gew.-% eines Anlagerungsproduktes von durchschnittlich 12 mol Ethylenoxid an ein Ci2/l4-Kok°sfettamin zugesetzt. Die Mischung wurde bei einer Temperatur von 31°C über eine Düse in ein Meßgefäß ge¬ spritzt, laufend umgepumpt und die sich einstellende Schaum¬ höhe über der flüsigen Phase abgelesen.Octanoic acid octyl 4,5EO ester 4 wt .-% water, dist. 62% by weight The formulation was as foam promoter to 6 wt .-% of an adduct of average 12 mol of ethylene oxide to a Ci2 / L4 Ko ° k s i n f ettam added to 0.25. The mixture was injected through a nozzle into a measuring vessel at a temperature of 31 ° C., pumped around continuously, and the foam height obtained was read off from the liquid phase.
Zum Vergleich wurde die Schaumentwicklung des Kokosamins-12 EO in Wasser (VI) sowie in einer Rezeptur beurteilt, die le¬ diglich 30 Gew.-% Triethanolamin und 4 Gew.-% Octansäure ent¬ hielt (V2). Die Ergebnisse sind in Tab.l zusammengefaßt.For comparison, the foaming of coconutamine-12 EO in water (VI) and in a recipe which only contained 30% by weight of triethanolamine and 4% by weight of octanoic acid were assessed (V2). The results are summarized in Tab. 1.
Tab.1: Schaummessungen in der SpritzapparaturTab. 1: Foam measurements in the spray gun
Legende: c(KA) = Konzentration Kokosamin-12EO Legend: c (KA) = concentration of coconut amine-12EO

Claims

Patentansprüche Claims
1. Endgruppenverschlossene Antischaummittel, dadurch er¬ hältlich, daß man Fettalkoholpolyglycolether der Formel (I)1. End group-sealed anti-foaming agents, obtainable by fatty alcohol polyglycol ethers of the formula (I)
R2R2
I R!θ-(CH2CHO)nH (I)IR! Θ- (CH2CHO) n H (I)
in der R für einen aliphatischen, linearen oder ver¬ zweigten Kohlenwasserstoffrest mit 1 bis 22 Kohlen¬ stoffatomen und 0, 1, 2 oder 3 Doppelbindungen, R- für Wasserstoff oder eine Methylgruppe und n für Zahlen von 1 bis 40 steht, in Gegenwart saurer Katalysatoren mit Carbonsäuren verestert.in which R represents an aliphatic, linear or branched hydrocarbon radical having 1 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R - is hydrogen or a methyl group and n is a number from 1 to 40, in the presence of acid Catalysts esterified with carboxylic acids.
2. Verfahren zur Herstellung von endgruppenverschlossenen Antischaummitteln, bei dem man Fettalkoholpolyglycol¬ ether der Formel (I)2. Process for the preparation of end-capped anti-foaming agents, in which fatty alcohol polyglycol ethers of the formula (I)
RR
I R10-(CH2CHO)nH (I)IR 1 0- (CH 2 CHO) n H (I)
in der R für einen aliphatischen, linearen oder ver¬ zweigten Kohlenwasserstoffrest mit 1 bis 22 Kohlen¬ stoffatomen und 0, 1, 2 oder 3 Doppelbindungen, R2 für Wasserstoff oder eine Methylgruppe und n für Zahlen von 1 bis 40 steht, in Gegenwart saurer Katalysatoren mit Carbonsäuren verestert. in which R represents an aliphatic, linear or branched hydrocarbon radical having 1 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R 2 represents hydrogen or a methyl group and n represents numbers from 1 to 40, in the presence of acid Catalysts esterified with carboxylic acids.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Fettalkoholpolyglycolether der Formel (I) einsetzt, in der Rl für Alkylreste mit 2 bis 18 Kohlenstoffatomen, R2 für Wasserstoff und n für Zahlen von 2 bis 10 steht.3. The method according to claim 1, characterized in that fatty alcohol polyglycol ethers of the formula (I) are used in which R 1 is alkyl radicals having 2 to 18 carbon atoms, R 2 is hydrogen and n is a number from 2 to 10.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man aliphatische oder aromatische, gegebenenfalls hy- droxysubstituierte Garbonsäuren mit 6 bis 22 Kohlen¬ stoffatomen einsetzt.4. The method according to claim 1, characterized in that one uses aliphatic or aromatic, optionally hydroxy-substituted carboxylic acids having 6 to 22 carbon atoms.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als saure Katalysatoren Mineralsäuren, Sulfonsäuren oder saure Ionenaustauscher einsetzt.5. The method according to claim 1, characterized in that mineral acids, sulfonic acids or acidic ion exchangers are used as acidic catalysts.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Veresterung bei Temperaturen von 80 bis 120°C durchführt und das Kondensationswasser kontinuierlich aus dem Gleichgewicht entfernt.6. The method according to claim 1, characterized in that one carries out the esterification at temperatures from 80 to 120 ° C and the water of condensation is continuously removed from the equilibrium.
7. Verwendung der endgruppenverschlossenen Antischaummit- teln nach Anspruch 1 zur Schaumregulierung in Wasch-, Spül- und Reinigungsmitteln, Lacken und Farben, als Hilfsmittel für die Zucker- und Hefeindustrie sowie in der Abwasserbehandlung von Kläranlagen. 7. Use of the end group-sealed antifoam agent according to claim 1 for foam regulation in detergents, dishwashing detergents and cleaning agents, lacquers and paints, as auxiliaries for the sugar and yeast industry and in the wastewater treatment of sewage treatment plants.
EP93915971A 1992-07-30 1993-07-21 Terminal-group-closed anti-foaming agents Revoked EP0652799B1 (en)

Applications Claiming Priority (3)

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DE4225236 1992-07-30
DE4225236A DE4225236A1 (en) 1992-07-30 1992-07-30 End-capped antifoams
PCT/EP1993/001938 WO1994003251A1 (en) 1992-07-30 1993-07-21 Terminal-group-closed anti-foaming agents

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EP0652799A1 true EP0652799A1 (en) 1995-05-17
EP0652799B1 EP0652799B1 (en) 1996-11-20

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DE19518476A1 (en) * 1995-05-19 1996-11-21 Basf Ag Pivalic acid esters of alkoxylated aliphatic alcohols
DE19802733B4 (en) * 1998-01-26 2006-08-24 Cognis Deutschland Gmbh & Co. Kg Anti-foaming agents
DE19940797A1 (en) 1999-08-27 2001-03-01 Goldschmidt Ag Th Obtained by Akoxylierung block copolymers, styrene oxide-containing polyalkylene oxides and their use
DE102005011608A1 (en) 2005-03-14 2006-09-21 Basf Ag Esterified alkyl alkoxylates as low-foaming surfactants
WO2009027456A2 (en) 2007-08-29 2009-03-05 Basf Se Esterified alkyl alkoxylates as solid low-foam wetting agents
WO2010108858A1 (en) * 2009-03-26 2010-09-30 Dr. W. Kolb Ag Component for deaerating a process water especially during paper production
WO2019023016A1 (en) * 2017-07-28 2019-01-31 Croda, Inc. Cleaning formulation comprising a solvent additive
CN118043304A (en) 2021-10-01 2024-05-14 科莱恩国际有限公司 End-capped bio-based low foaming surfactants

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DE3800492A1 (en) * 1988-01-11 1989-07-20 Henkel Kgaa FOAM CONTROL AGENT FOR THE PRODUCTION AND PROCESSING OF FOODSTUFFS OR FOR FERMENTATION PROCESSES
IL95029A0 (en) * 1989-07-12 1991-06-10 Gaf Chemicals Corp Low viscosity defoaming/antifoaming formulations
DE4041754A1 (en) * 1990-12-24 1992-06-25 Henkel Kgaa USE OF SPECIAL CARBONIC ESTERS AS A FOAM CONTROL

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See references of WO9403251A1 *

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JPH07509180A (en) 1995-10-12
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DE59304555D1 (en) 1997-01-02
ES2093975T3 (en) 1997-01-01
ATE145346T1 (en) 1996-12-15

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